Alkylation of paraffin hydrocarbons



Patented Dec. 3, 1946 UNITED STATES PATENT orrlca ALkYLA'rIoN or rmarm I HYDROCARBONS Arlstid v. Grosse, Bronxvllle, N. Y., and Carl B.

Linn, Chicago, Ill., asslgnors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application May 18, 1942, Serial No. $3,490

6 Claims.

This is a continuation-in-part of our co-pending application Seral No. 299,108, filed October 12,

This invention is concerned with the interaction of isoparafllnic hydrocarbons with ethylene in the presence of catalysts. It is more specifically concerned, with a simple and easilyregulated process involving the use of mixtures of normally liquid and normally gaseous compounds of fluorine which catalyze the desired conversion with a h gh degree of efllciency'and undergo substantially n alteration in the course of the reactions.

Processes for the formation of higher molecular weight isoparafilnic hydrocarbons from isobutane, isopentane, and other alkylatable parafllnic hydrocarbons, .all herein included by the term isoparafllns, are important from the standpoint of the motor fuel industry which demands increasing quantities of isoparafilns boiling in the range of gasoline motor'fuel.

In one specific embodiment the'preserit invention comprises a process for synthesizing parafflnc hydrocarbons by reacting an lsoparafllnic hydrocarbon with ethylene under alkylating conditlons in the presence of hydrogen fluoride boron fluoride.

Considerable quantities of butanes and lighter gases containing ethylene are available as byproducts-from the cracking of petroleum fractions to produce relatively high primary yields of gasoline, and by segregation of butanes and v ethylene by relatively simple iractional'distilla- 1 tion methods. cuts are available-for recombina come by the use of the mixed boron fluoride-by drogen fluoride catalyst of the present invention. Sulfuric acid, for example, has a tendency to oxidize hydrocarbons with the formation of sulfur dioxide. Phosphoric acid can be utilized as catalyst for the alkylation of isoparafllnic hydrocarbons but the reaction is not accelerated to a practical degree'unless high temperatures and pressures are employed. Aluminum chloride and similar metal halides which are generally 5 drogen fluoride,

(onto-cam) I 2 I employed in the presence 01 hydrogen chloride or hydrogen bromide have the'usual disadvantages'inherent to the use of solid granular catwas in ,that the efficiency of the reaction is to some extent dependent upon the fineness of the subdivision of the catalyst, the emciency of stirring or mixing of the reaction mixture, etc. The

recovery of aluminum chloride .or other metal halides from the reaction products in suitable form for recycling is difficult and expensive whereas the present catalyst mixture of boron fluoride and hydrogen fluoride is readily separable in a form which can be recycled to further use in the alkylation reaction.

Thus considerable difllculties have been encountered previously in attempting to alkylate isoparaillnic hydrocarbons with ethylene in the presence of such catalysts assulfuric acid or hydrogen fluoride of about ,90 to about 100% con-, centration, but we flnd that the reaction between ethylene and an lsoparafiln such as isobutane, isopentane, lsohexane, etc., or between ethylene and isoparafiln-normal paraflln mixtures may be carried out readily in the presence of a mixture of boron fluoride and hydrogen fluoride to give a relatively high yield of substantially saturated hydrocarbons comprising essentially branched chain hexanes, heptanes, octanes, and

higher boiling isoparafflns. The catalyst utilized in thepresent invention is formed by mixing boron fluoride with hydrogen fluoride. The former is a gas at normal temperatures and boils at -'101 C. under atmospheric pressure 'while substantially anhydrous hydrogen fluoride is-a liquid boiling at about 20- c. under an absolute pressure of 1 atmosphere.- A mixture of boron fluoride and hydrogen fluoride can be used as alkylating' catalyst in apparatus which has been cooled to maintain a temperature the boiling point of hydrogen fluoride and low slightly below enough to keep in liquid state a substantial proportion ofthe cat'alyst, or the catalyst mixture can be used at higher temperatures if sufllcient pressure 'is' kept upon the'apparatus. By main;

taining an excess of isoparafllns to olefins at all times, polymerization reactions and the formation of ethyl fluoride are kept relatively low so that the products consist principally of alkylated derivatives of the original isoparaflln hydrocarbon.

The process ofthe present invention maybe carried out utilizing either batch or continuous .typ'e operations. In batch type operation the preferredprocedure is to agitate a mixture of hyboron fluoride, and an isoparamn and to introduce gradually thereto ethylene, an

ethylene-ethane fraction, a mixture of ethylenev and an'isoparaflln, or a mixture of a normal paraffin, an isoparaflin and-ethylene. time of mixing suflicient to eiiect substantially complete reaction of the ethylene with the isoparaflin, the latter being present in excess of the olefin at all times, the agitation is stopped and the reaction mixture is separated into catalyst, unconverted isoparafiin, and alkylation product,

after which the excess isoparailln and used cata lyst may be utilized in a subsequent alkylation treatment.

' The process may be made continuous by pro-. viding a mixing zone through which the reacting hydrocarbons and catalyst are passed and in After a.

which was operated while ethylene was introduced at 20 C. to a total pressure of 35 atmospheres. 'I'he stirring at 20 C. was continued for about 12 hours after which the reaction mixture was removed from the autoclave and separated into unconverted isobutane, hydrogen fluorideboron fluoride catalyst, and about 200 parts by stantially saturated hydrocarbons containing 90% which suflicient time is given for the completion of the desired alkylation. The products from such a reaction zone are then directed to a separating zone in which the desired alkylation products are separated from unconverted isoparafiln's and catalyst components. The recovered unconverted isoparafiins and catalyst are then recycled to further contact with the isoparafllns and ethylene being charged to the process.

The activity of a boron fluoride-hydrogen fluoride catalyst is dependent upon the relative proportions of these materials forming thecatalyst mixture. The diiferent catalytic composites which may-be utilized are not necessarily equivalent in their action particularly when diiferent isoparafiins are alkiated by ethylene. While alkylation reactions occur at temperatures of from about 30 to'about 100 C., the use of a temperature of between about 0 and about 50 C. is

preferred. Pressures utilizable may vary from weight of an alkylation product consisting of subby volume of gasoline with an end boiling-point of 205 C. The gasoline fraction contained about 55% by volume of branched chain hexanes.

The foregoing specificationand example indi cate the character and practical value of the present invention, although it is not intended that either section should impose undue limitations thereon.

We claim as our invention:

1. A process for the production of normally liquid saturated hydrocarbons which comprises reacting an isoparaflin with an olefin under alkysubstantially atmospheric to approximately 50 atmospheres or more. In .order to obtain high yields of alkylation product with substantially no formation of olefin polymers, it is desirable to maintain a molar excess of isoparaflin to olefln throughout the entire reaction. Generally up to about 25molarproportions of isoparaflins are,

present per molecular proportion of olefin introduced to alkylation. The amount of olefin polymerization is thus not only kept low but the formation of ethyl fluoride is also kept low so that the reaction product consists principally of alkylated derivatives of the original isoparafiin containing relatively small amounts of ethyl fluoride.

The following example shows results obtained when utilizing the present process for alkylating an .is'oparaflinic hydrocarbons wlth'..,ethylene although the example given should. 'not be construed to impose undue limitations upon the generally broad scope of the invention.

100 parts by weight of. hydrogen'fluoride, 10'

parts by weight of boron fluoride, and 300 parts by weight of isobutane were charged to an auto-U clave provided with a mechanically driven stirrer 'tion of boron fluoride.

lating conditions in the'presence of an alkylation catalyst consisting essentially of a major proportion of hydrogen fluoride-and a minor propor- 2 A process for the production of normally liquid saturated hydrocarbons which comprises reacting an isoparaflin with ethylene under alkylating conditions in the presence of an alkylation catalyst consisting essentially of a major proportion of hydrogen fluoride and a minor proportion of boron fluoride.

3. A process for synthesizing hydrocarbons which comprises reacting an isoparaflin with an olefin under alkylation conditions in the presence of a metal-free alkylating catalyst predominatin in hydrogen fluoride and containing a minor proa portion of boron fluoride.

minor proportion of boron fluoride.

4. A process for synthesizing hydrocarbonswhich comprises reacting an isoparaflln with ethylene under alkylation conditions in the preseuce of a metal-free alkylating catalyst predominating in hydrogen fluoride and containing a minor proportion of boron fluoride. I 5. A process for the production of normally anrs'rm v. GROSSE. CARL 13. mm. 

